Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Mixed-integer nonlinear approach for the optimal scheduling of a head-dependent hydro chain

This paper is on the problem of short-term hydro scheduling (STHS), particularly concerning a head-dependent hydro chain We propose a novel mixed-integer nonlinear programming (MINLP) approach, considering hydroelectric power generation as a nonlinear function of water discharge and of the head. As a new contribution to eat her studies, we model the on-off behavior of the hydro plants using integer variables, in order to avoid water discharges at forbidden areas Thus, an enhanced STHS is provided due to the more realistic modeling presented in this paper Our approach has been applied successfully to solve a test case based on one of the Portuguese cascaded hydro systems with a negligible computational time requirement.

Tetranuclear COPPER(II) complexes with macrocyclic and open-chain disiloxane ligands as catalyst precursors for hydrocarboxylation and oxidation of alkanes and 1-phenylethanol

Two new tetranuclear complexes [Cu-4(mu-O)(L-1)-Cl-4] and [Cu-4(mu(4)-O)(L-2)(2)Cl-4] (2), where H2L1 is a macrocyclic ligand resulting from [2+2] condensation of 2,6-diformy1-4-methylphanol (DFF) and 1,3-bis(aminopropy1)tetramethyldisiloxane, and HL2 is a 1:2 condensation product: of DFF with trimethylsilyl p-aminobenzoate, have been prepared. The structures of the products were established by Xray diffraction. The complexes have been characterised by FTIR, UV/Vis spectroscopy, ES1 mass-spectrometry and magnetic susceptibility measurements. The latter revealed that the letrftriuclear complexes can be descr bed as two ferromagnetically coupled dinuclear units, in which the two copper(II) ions interact antiferromacinetically. The ccimpi.iunds act as homogeneous catalyst precursors for a number of single-pot reactions, including (I) hydrocarbaxylation, with CO, H2O and K2S2O8, of a variety of linear and cyclic (n = 5-8) alkanes into the corresponding Cn+1 carboxylic acids, (ii) peroxidative oxidation of cyclohexane, and (iii) solvent-free microwave-assisted oxidation of 1-phenyletha.nol.

On chaos, transient chaos and ghosts in single populations models with allee effects

Density-dependent effects, both positive or negative, can have an important impact on the population dynamics of species by modifying their population per-capita growth rates. An important type of such density-dependent factors is given by the so-called Allee effects, widely studied in theoretical and field population biology. In this study, we analyze two discrete single population models with overcompensating density-dependence and Allee effects due to predator saturation and mating limitation using symbolic dynamics theory. We focus on the scenarios of persistence and bistability, in which the species dynamics can be chaotic. For the chaotic regimes, we compute the topological entropy as well as the Lyapunov exponent under ecological key parameters and different initial conditions. We also provide co-dimension two bifurcation diagrams for both systems computing the periods of the orbits, also characterizing the period-ordering routes toward the boundary crisis responsible for species extinction via transient chaos. Our results show that the topological entropy increases as we approach to the parametric regions involving transient chaos, being maximum when the full shift R(L)(infinity) occurs, and the system enters into the essential extinction regime. Finally, we characterize analytically, using a complex variable approach, and numerically the inverse square-root scaling law arising in the vicinity of a saddle-node bifurcation responsible for the extinction scenario in the two studied models. The results are discussed in the context of species fragility under differential Allee effects. (C) 2011 Elsevier Ltd. All rights reserved.

Scaling law in Saddle-node bifurcations for one-dimensional maps: A complex variable approach

The study of transient dynamical phenomena near bifurcation thresholds has attracted the interest of many researchers due to the relevance of bifurcations in different physical or biological systems. In the context of saddle-node bifurcations, where two or more fixed points collide annihilating each other, it is known that the dynamics can suffer the so-called delayed transition. This phenomenon emerges when the system spends a lot of time before reaching the remaining stable equilibrium, found after the bifurcation, because of the presence of a saddle-remnant in phase space. Some works have analytically tackled this phenomenon, especially in time-continuous dynamical systems, showing that the time delay, tau, scales according to an inverse square-root power law, tau similar to (mu-mu (c) )(-1/2), as the bifurcation parameter mu, is driven further away from its critical value, mu (c) . In this work, we first characterize analytically this scaling law using complex variable techniques for a family of one-dimensional maps, called the normal form for the saddle-node bifurcation. We then apply our general analytic results to a single-species ecological model with harvesting given by a unimodal map, characterizing the delayed transition and the scaling law arising due to the constant of harvesting. For both analyzed systems, we show that the numerical results are in perfect agreement with the analytical solutions we are providing. The procedure presented in this work can be used to characterize the scaling laws of one-dimensional discrete dynamical systems with saddle-node bifurcations.